Anthracene dye and a process of manufacture



Patented Aug. 17, 1 926.

UNITED STATES PATENT OFFICE.

IVAN GUIBELMANN, OF SOUTH MILWAUKEE, WISCONSIN, ASSIGNOB TO THE NEWPORTCOMPANY, OF CARROLLVILLE, WISCONSIN, A CORPORATION OF DELAWARE.

ANTHRACENE DYE AND A PROCESS OF MANUFACTURE.

No Drawing.

This invention relates to coloring matters of the anthracene series anda process of making the same, more particularly to the coloring mattersobtained by the conden-' I sation of a halogenated pyranthrone body withcarbazole.

By pyranthrone is meant the coloring matter obtained by heating2,2-dimethyl- 1,1'-dianthraquinonyl. This coloring matter dies cottonfrom a hydrosulfite vat in violet shades, yielding orange shades onoxidation. It is known in the chemical arts as pyranthrone and shallhereinafter be referred to by this name.

16 The condensation reaction between the halogenated pyranthrone bodyand carbazole results in a coloring matter of the type R R in which Rrepresents the pyranthrone complex and R" the carbazole radicle 20 andin which the pyranthrone complex is linked to the nitrogen atom of thecarbazol radicle, and in the formation of a halogen acid. The reactionproceeds best in the presence of a high boiling solvent, at temperaturesranging between 150 and 210 C.

Application filed Kay 9, 1925. Serial No. 29,216.

illustrate my invention in a preferred form, but I do not wish to limitthe process to these examples:'

Example 1.--Suspend 50 parts by weight of finely grounddibrom-pyranthrone in 600 parts by Weight of dry nitrobenzol. Add 20parts by weight of carbazole, 25 parts by weight of anhydrous sodiumacetate, in the form of a fine powder, and 10 parts by weight of basiccopper acetate as a catalyzer. Heat the mixture under agitation to 200C. for a period of 20 hours. The color of the mixture changes graduallyto a dark brown. Cool the reaction mass to 60 C. and add 400 parts byweight of denatured alcohol. Stir the mixture for 1 hour and filter offthe brown reaction product. Wash the filter cake with denatured alcoholand hot Water until the solvent and the inorganic salts have beeneliminated. After drying and grinding, the reaction product constitutesa red-brown powder which, from a hydrosulfite vat, dyes cotton a violetshade whlch oxidizes to a rich brown shade on ex posure to air or othersuitable oxidizing Neutralizing agents, such as anhydrous soage ts 'diumacetate or sodiumvcarbonate, and catalyzers, such as basic copperacetate, may be used to facilitate the reaction.

The following examples will serve to The product of the reaction betweendibrompyranthrone and carbazole is probably best represented by thefollowing chemical formula:

The exact position of the bromine atom remaining in the pyra-nthroneradicle and of the coupling bond is not known. The second bromine atomunites with one hydrogen atom from the amino group to form hydrobromicacid.

Eocample 2.Suspend parts by weight of finely ground dichloryranthrone in600 parts by weight of nap thalene. Add 25 parts by weight of carbazole,25 parts by Weight of anhydrous sodium carbonate in the form of a finepowder, and 5 parts by weight of basic copper acetate as catalyzer. Heatthe mixture under agitation to 200 C. for a period of 20 hours. Thecolor of the mixture changes gradually from red to dark brown. Pour thereaction mass into 500 parts by weight of water and remove thenaphthalene completely by steam distilation. Filter oil the remainingbrown product and wash the filter cake thoroughly with hot water toremove inorganic salts. After drying and grinding, the reaction productforms a brown powder which dyes cotton from a hydrosulfite vat a violetshade which oxidizes to a rich brown shade on oxidation with well-knownoxidizing agents used in the dyeing of vat colors.

While the temperature specified in the above examples is 200 C. I havefound that, by varying the temperature above and below 200 C. variousshades of product ranging from reddish-brown to yellowishbrown areobtained. The coloring matters thus obtained give shades on dyeing thatare extremely fast to washing, light and other influences. The coloringmatters themselves are insoluble in hot and cold water, sparinglysoluble in dilute acids and organic solvents, but usually more so inorganic high boiling solvents. They dissolve 1n concentrated sulfuricacid, givlng a blue to purple color, and they are precipitated out againon dilution with water. They are, however, easily soluble in alkalinehydrosulfite solution.

Halogen I am aware that numerous details of the process may be variedthrough a wide range without departing from the spirit of thisinvention, and I do not desire limiting the patent granted. other thanas necessitated by the rior art. a

I claim as my invention:

1. The processof producing coloring matters of the anthraoene series,which consists in heating a halogenated pyranthrone body with carbazolein the presence of a high boiling solvent and a neutralizing agent.

2. The process of producing coloring matters of the anthracene series,which consists in heating a halogenated pyranthrone body with carbazolein the presence of a high boiling solvent, a neutralizing agent andcopper salts.

3. The process of producing coloring matters of the anthracene series,which consists in heating dibrom-pyranthrone with carbazole in-thepresence of a high boiling solvent and a neutralizing agent.

4. The process of producing coloring matters of tlie anthracene series,which consists in heating dibrom-pyranthrone with carbazole in thepresence of a high boiling solvent, anhydrous sodium acetate as aneutralizing agent and a catalyst.

5. As new articles of manufacture, the coloring matters of theanthracene series which are obtained by heating a halogenatedpyranthrone body with carbazole.

fis-As new articles of manufacture, the coloring matters of theanthracene series which are obtained by heating a br'o'minatedpyranthrone body with carbazole- 7. The process of producing coloringmatters of the anthracene series, which consists in heating ahalogenated pyranthrone' body with carbazole.

8. As new articles of manufacture, coloring matters of the anthraceneseries havin most probably the following genera formula:

said coloring matters being in general red brown powders, which from ahydrosulfite vat, dye cotton a violet shade, which shade oxidizes to arich brown shade on exposure to air or other oxidizing agents.

9. As new articles of manufacture, coloring matters of the anthraceneseries having most probably the following formula:

11. Materials dyed with coloring matters described in claim 9.

In testimony whereof I have hereunto 20 subscribed my name.

IVAN GUBELMANN.

